Monoazo dyestuffs



Patented Jan. 16, 1951 U TED S ENT OF oNoAzo nYns'r FEs- Willi Widmer,i-nottnimgengand Rudolf ,Rueg f asel, Switzerland, ,assignors to GibaLimited, ,Bas'el,,Switzer1and"' j -No Drawing. "Application September'7, 1948, Se-

' rial No. 48,152. I lmswitzerland scptcmber 24,

Accordingto this invention ,valuable newfniono azo-wdyestufis-are madeby coupling amaze-compound often amine of the general iormula v ziclam y(cited-198) 2 desired, additional substituents may be introduced intothe benzene nucleus-after the aforesaid condensation, or substituentsalready present may'be'replaced by or-converted into other 5substituents. 3k The amines of the general formula first inen- SNH -.Rationed above, which are used as starting'mate- 0 \j, rials formaking'the-azo-dyestufis of the "invenin which R1 represents an aromaticnucleusmf the benzene series, and R2 represents. an aliphatichydrocarbonradical of 8-12 carbon atoms, with a coupling componentcontaining a sulfpnic acid group; p a

The amines ofthe above general formulacan be obtained bymethods inthemselves known irom'compounds of the general formula tion, contain asthe radical R2 an aliphatic' hydrocarbon radical of -8-12 carbon atoins;aliphatic radical may also contain cyclic bonds. There may be mentionedthe following radicals: octyl, nonyl, decyl, undecyl or dodecyl groups.

' As examples of amines of the general formula first given above theremay be mentioned the following -(in-this,list the sulfonalkylamidesgroupdenotes an SQ2NHCnl-Izn+1.group, in which. the

alkyl group CnH2,n +1 is advantageously an nnbranched aikyigroun' d n sea than"? SOTQNH?B2 and less than 13, for example, a sulion-n-octyl inwhich R1 and R2 have the meanings given above and Y represents asubstituent convertible into an --NH2 group, by converting the"substituent Y intoan '-,NH2 group. Thecompounds amide, asulion-nedecylor dodecyl-amide etc, .see the ;-last ,sentence .of thepreceding para,

, rap

of the last mentioned formula can he obtained eral formula H2NR2 (inwhich R2 represents anali-phatic hydrocarbon radical-of 81 hon atoms)and, when the radical R1 contains no substituent convertible intoan--=NHz group, in-

'troducing such a substituent into the radical R1 afterthe condensation.One-form of the above described process for making such intermediateproducts is, 'forex-r ample, the following: A nitrobenzene sulfonic acidghalide or an acyl'aminobenzene sulfoni'c acid 3- or -4-aminobenzenel-sulfonalhylamides, 4-alkox'y- "(for -example, ethoxyor methoatyhi iaminobenzene-1-sulfonalky1amides, I Y e-a lkonylfor example, methoxy-d-waminobenzene iesulfonalkylamides,i6-clilor0-"3-aminobenzene-"1-sulfonalkylamides,

4-methyl 3 aminobenzene-l-sulfonalkylamides, and 6-methyl 3aminobenzene-rl-sulfonalkylamides.

The monoazo-dyestufis. obtainable by their:- vention contain one or moresulfonic acid group The coupling components used for making thesedyestufis may, 'inother' respects, be any halide condensed withanaliphatic amine containing 8-12 carbon atoms, and the group present inthe condensation product is reduced toan -NH2 group or, the *aoylaminogroup is h-ydrolysed. The condensation may be conducted in an anhydrousor aqueous medium,

be usedlas starting materials; which containyno further substituentsin"the benzene nucleusgr which contain further snb'stituents',forexampl'e', halogen atoms, such as chlorine, or'alkqxygronps such asethoxy or especially methoxygroups; If

examples of coupling components suit ble for making monoazo-dyestufi's"by the present invention there may be mentioned: I 'C'ompounds of thenaphthalene series Hydroxynaphthalene ,monesulfonic acids such asl-hydroxynaphthalene-4 su1f0nic acid, hy droxynaphthalene disulfonicacids suchas 1 326 v 3 1:3:8-,1:4:8-, 2:3:6, or lenedisulfonic acid;aminonaphthalene monosulionic acids such as 226-, 2:7- or2:8-aminonaphthalenesulfonic acid; aminonaphthalenedisulionic acids suchas, 2:4:7- 2 ;'7- or 2:6:8 aminonaphthalenedisulfonic acid;- amino',alkylamino-, arylamino or acylamino hydroxynaphthalene 2:6:B-hydroxynaphthasulfonic acids and disulfonic acids such as 2:8:6-,: or2:6 :8 amino-hydroxynaphthalene sulfonic I acid,1-phenyl-amino-8-hydroxynaphthalene-4 droxynaphthalene sulfonic -aoid;1-acety1amino-,-

1-benzoylamino-, lpara-toluene-sulfonylamino-, l-phenoxy-acetylaminoor1- (2'-chloro-P noxy) acetylamino-B-hydroxynaphthalene-3:6-;

disulfonic acid; l-acetylaminoor l-para-toluenesulfonylamino-8-hydroxynaphthalene-4:6-.

disulfonic acid.

I Pym l s p sulfo)-phenyl-3-methy1-5- pyrazoe l-lzl'r-m-ethyl-e'-sulfo)-phenyl-3-methyl -5 pyrazolone;

l 2fchloroy-sulfo) -phenyl-3-rnethyl- 5 I 15 :5, -disulfo) pheny1 3methyl 5 pyrazo- 19 1 (8' sulf o-2'-naphthy1)-3methyl -5 pyrazolQ fi'l-1'- 3;' -Sl11f0phenyl)-5 pyrazolone 3 carboxylic ac id...- ilffIhe;mines of the formula first mentioned above may-be diazotized by methodsin'the'rhjelves-' known. The diazotization is advantageouslyconducted'inthe presence of a'suitable which 3.1 represents an aromatic nucleus ofithe benzene series, R2 represents an aliphatic hydrocarbon radical of8-12 carbon atoms, and R3 represents the radical of a coupling compo--nent. They can be used for dyeing or printing averywide variety ofmaterials.

These monoazo-dyestufis containing'a- -sulfonic .acidgroup are suitableprincipally for. dyeing animaL-fibers such as leather, silk andespecially solution-promoter, for example, ethyl alcohol.

of hot ethyl alcohol and, after cooling it to about 40 C., the solutionis mixed with 7 parts of hydrochloric acid of 30 per cent. strength. Asaturated solution of 1.4 parts of sodium nitrite is introduced dr'cipwise at 10-15 C; 1

the' yellow' dyestuff is removed from the coupling mixtureand dried. Itis a yellow powder which dyes wool pure yellow tints from an acetic acidbath. The idyeings are distinguished by ,very

good properties of fastness to alkali and Washing.

By using 1- (2 :5 -disulfo) -phenyl-3-methyl-5- pyrazolone, instead ofl-(2-chloro-5-sulfo)- phenyl-3-methyl-5-pyrazolone, a dyestuff havingsimilar properties is obtained. The 4- metho xy- 3aminobenzene-l-sulfon-n-dodecylamide "used as"a"'starting material inthis example may be prepared; for example, in the following manneri4-methoxy-3-nitrobenzene-l-sulfonyl chloride is condensed in thepresence of pyridine with n-dodecylamine, and the resulting l-methoxy-3-nitrobenzene-1-sulfon-dodecy1amide is reduced in alcoholic solutionwith iron and hydrochloric acid to form4-methoxy-3-aminobenzene-1-sulfon-n-dodecylamide. j

A diazo solution prepared from-7.5" parts of 4- ,methoxy-Baminobenzene-lesulfon.- n dodecylamide obtained as described in thefirst paragraph QffEXQl'IlDlQ 1 is coupled at 0- C. with a solution of'7 parts of the, disodium salt of 2 hydroxynaphthalene-6:8-disulfonicacid in parts of a saturated solutionjof sodium carbonate, and thecoupling is brought to completion by the addition ,ofa small-quantityof. sodium hydroxide solution. The dyestufi. is precipitated by theaddition of sodium..chloride, removed by filtration and dried. 'Itis aredpowder'which dyes wool very pure orange tint's from acetic-acidbaths. The dyeings are .-distinguished -by,..very good; properties offastness'to alkali and washing.

i A Example}; "l diazo .solutionprepared from 7.5 parts of .aemethoxy-ipaminobenzene l-sulfon-n-dodecylamide as described in the-first paragraphof Example l is coupled at 0 C. with a s0lution of 7':parts of thedi-sodium salt of l-hydroxynaphthalene-3z6-disulionic acid in 60 partsof a satu wool; and also for dyeing artificial fibers of.superpolyamides or superpolyurethanes. The dyeings obtainable therewithare distinguished by the very special purity andbrightness of theirtints. and. also by very good properties of fastf:

ness to alkali and Washing. I

v The following examples illustrate the invention, the parts being byweight:

\ I Erii tmplel 7.5 parts Jof -methoxy-3-aminobenzene4sulfon-n-dodecylamide are dissolved in 30 parts rated solution ofsodiumcarbonate. When the coupling is finished the dyestuff is removedbyfiltration and dried. It is a red powder which dyes Wool verypureyellowish red tints irpm an aceticacid'bath. The dyeings aredistinguished by very good propertiesof fastness to alkali and wash H .IByusing l-hydroxynaphthalene 4 sulifonic .acid,ins tead ofl-hydroxynaphthalene-B 6-disu-lionic acid, a dyestuffi. having similarproperties obtained. HEIampZQQY:l.".

. WA -diazo solution prepared a T715 .4smethoxy-3 amincbenzene-1-sulfon-n-dodecyl;

amide asdescribed in thefirst, paragraph of Ex.- .amplelis coupled at 0.-C with a solution of lodl'parts ofthe disodium salt of l-para-tolueneesulfonylaminor-S-hydroXynaphthalene-3; 6-. disul; :fe ie add n 6. ar bfated l i sodium carbonate. Afterafew Hours the can:

arisen) pling is complete. The dyestufi is removed byfiltrationand'dried. it. is a red powder Which dyes wool very purebluish-red tints from an acetic acid bath.

By using 4-methyl-3-a nino-l-sulion-n-dodecylamide, instead of4-methoxy-3-methylbenzenel-sulfon-n-dodecylamide, a dyestufi is obtainedwhich yields somewhat more yellow tints on wool.

FWD?

34 parts of 3-aminobenzene-l-sulfon-n-dodecismi-iie dissolved in" "80-parts or hot ethyl ar'oohoi and mixedat the'bdil'ing pointwithaconcenratedadu'e'ous solution'of7.5fparts of sodium nitrite? "The solution,which is'" homogeneous when hot, is introduced dropwise 'at atemperature-below 1'0"-.C. into amixture' of 6.7partsof hydrochloric acid of 30.percent;strength'andZOO parts a of ethyl alcohol. After dilution withwater there is obtained a clear somewhat brownish colored diazo solutionwhich is then stirred with 2 parts of urea for 1 hour atom-20 C. inorder to decompose the excess of nitrous acid.

The diazo solution obtained in the above manner is coupledatjflff Q.with a solution of 28 parts of the sodium salt of 1-(fl siilfo)-phenyl-3- meth l- 5 -pyragol9 ne in 500 parts of a saturated solu'fgitsogliii carbonate. The yellow dyestu'fi' which forms immediately isremoved by filtration after a few hours, and is then dissolved in hotwater. The aqueous'soluti-on is filtered,

if necessary;and then mixed withsodium chloride offastnssto Washing andlight. 7 Bynsing' fi-methyl g-aminobenzene-l-sulfon- 7 n-dodec'yl'amide,instead of"3'-aminobenzene-'1- "sumo-h; dodecylamide," a dyestuffhavingsimilar bropertiesis obtained.

36parts of 6emethyl-3-aminobenzeneel-sulf'onn-'idodecylamide aredissolvedfin'80 parts of hot ethyl alcohol and mixed at a raisedtemperature with a concentrated aqueous solution of 7.5 parts of sodiumnitrite. The homogeneous solution is introduced dropwise, whilethoroughly stirring and cooling below 10 C. into a mixture of 160 partsof ethyl alcohol and 6'7 parts of hydrochloric acid of 30 per cent.strength. Upon dilution with water a clear diazo solution is obtainedwhich is stirred for 1 hour longer at 10-20" C. with 2 parts of urea. j

The diazo solution so obtained is coupled at 0 C. with a solution of 38parts of the disodium salt of l- (2 :5'-disulfo)-phenyl-methyl-5-pyrazclone in 500 parts of a saturated solution ofsodium carbonate. The yellow dyestuff which forms immediately isisolated after a few hours by the addition of sodium chloride and dried.The dyestufi is obtained in the form of a brownish orange resinous mass,which dissolves in water with a green yellow coloration. From an aceticacid bath this dyestuff dyes wool level green yellow tints having verygood properties of fastness to washing and light.

By using 1-(2'-chloro 5' sulfo) -pheny1-3- methyI-S-pyrazolone, insteadof 1-(2:5'-disulfo)-phenyl-3-methyl-5-pyrazolone, a dyestufi havingsimilar properties is obtained.

which is 'stirred forlhour" with2parts of urea. The resulting diazosolution is mixed at 0} Q. with solution of 35 parts of the dish "saltof 2-hydroxynaphthal'ene 6 :s-oishuoh I 500 parts of a saturated's-olutioir of sodi bonate. The resulting red orange dystufi *1 latedafter afewhours and dissolvdihhot w The solution is filtered to removesmall quan s of impurities, if desired, and then mixed with a sufiicientquantity of sodium chloride to reprecipitate the bull; or the dyestufi Te dy' t is removed by filtration and dried. A 'd obtained whichdissolves ifrwater wit an coloration and dyes wool yellow orahge ti anacetic acid'bath. 7

sulfon-n-dodecylamide a dyestufi havihg s properties is obtained.

37.5 a parts of fi-chlo ofiaminobenzene-l-sulf on-n-dodecylamideare"dis"solved in '75 parts of ethyl alcohol at a raised temperature andthen mixed with a concentrated" 7.5 partsof sodium nitrite. solution isintroduced, while thlor and. cooling below 0 0., into parts of ethylalcohol and 6 rifc acid of 30 per cent. St, with water a clear diazo Y,which is stirred with "2 "parts of ur a e ii i The resulting diazosolutionis epuple a I) with a solution of 2s part's'b'f thos'odiiimkahof 1-(4-sulfo) -phenyl-=3-methyl-5-pyrazolone in 500 parts of asaturated solution of sodium carbonate. The yellow dyestufi which formsimmediately is removed by filtration after a few hours and thendissolved in hot water. The solution is filtered and the dyestuif isprecipitated by the addition of sodium chloride, removed by filtrationand dried. A yellow powder is obtained which dissolves in water with ayellow coloration and dyes wool from an acetic acid bath yellow tintswhich are very fast to washing.

Exampie 9 29 parts of 3-aminobenzene-l-sulfon-n-octylamide are dissolvedin parts of hot alcohol and .mixed with a saturated aqueous solution of7.5

parts of sodium nitrite. The solution is introduced dropwise at atemperature below 10 C. into a mixture of parts of ethyl alcohol and 67parts of hydrochloric acid of 30 per cent. strength. The alcoholic diazosolution is mixed with a solution of 2 parts of urea in 200 parts ofwater and the whole is stirred at 15 C. until an excess of nitrous acidis no longer present.

2'7 parts of the sodium salt of 2-amino-8- hydroxy-naphthalene-6-sulfonic acid are dissolved in 250 parts of water and then introduceddropwise in the course of 1 hour at 20 C. into the diazo solutiondescribed above. After 20 hours the crude dyestuff which precipitates isisolated, dried and dissolved in 200 parts of ethyl alcohol. The. deepred solution is filtered to remove impurities, the alcohol beingdistilled oil? by the introduction of steam. After the addition ofsodium chloride the dyestuff is removed by filtration and dried. A redpowder is obtained which dissolves in water with a red coloration anddyes wool fast red tints.

By using 3-aminobenzene-l-sulfon-n-decylamide instead ofB-aminobenzene-l-sulfon-noctylamide a dyestuff having similar propertiesis obtained.

By using 2-amino-naphthalene-fi-sulfonic acid instead of 2amino-8-hydroxynaphthalene-6- sulfonic acid, there is obtained a yelloworange dyestufi which dyes wool fast yellow orange tints.

- Example 10 Example 11 1.5 parts of the dyestufi obtained as describedin the first paragraph of Example 3 are dissolved in 4000 parts ofvwater, 10 parts of crystalline sodium sulfate are added to the dyebath,and 100 parts of well wetted wool are entered at 49 50 C. There are thenadded 4 parts of acetic acidof 30 per cent. strength, the whole isbrought to the boil in the course of 30 minutes and dyeing is carried onfor 45 minutes at the boil. The wool is then rinsed and dried. It isdyed a very pure scarlet red tint.

I 8 What is claimed is 1. A monoazo dyestufi of the formula in which Xstands for a member selected from the group consisting of hydrogen,chlorine, methyl and methoxy, R2 stands for an aliphatic hydrocarbonradical .of 8 to 12 carbon atoms, and R3 stands for the radical ofan'aminonaphtha- 1ene sulfonic acidbound to the azo group in a positionvicinal to the amino group.

2. The monoazo-dyestuff which in its free acid state corresponds to theformula Nfim-cang 03H 0 o I WILLI WIDMER.

, RUD L RUEGG. I

. REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Great Britain Jan. 12, 1939

2. THE MONOAZO-DYESTUFF WHICH IN ITS FREE ACID STATE CORRESPONDS TO THEFORMULA